EP2258465B1 - Filtre en céramique - Google Patents
Filtre en céramique Download PDFInfo
- Publication number
- EP2258465B1 EP2258465B1 EP09723963.6A EP09723963A EP2258465B1 EP 2258465 B1 EP2258465 B1 EP 2258465B1 EP 09723963 A EP09723963 A EP 09723963A EP 2258465 B1 EP2258465 B1 EP 2258465B1
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- EP
- European Patent Office
- Prior art keywords
- membrane
- titania
- porous
- ceramic
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000919 ceramic Substances 0.000 title claims description 71
- 239000012528 membrane Substances 0.000 claims description 269
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 248
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 96
- 239000000758 substrate Substances 0.000 claims description 83
- 239000011148 porous material Substances 0.000 claims description 57
- 239000000377 silicon dioxide Substances 0.000 claims description 48
- 238000000108 ultra-filtration Methods 0.000 claims description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000001471 micro-filtration Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 description 25
- 238000000926 separation method Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000010304 firing Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- 238000005204 segregation Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000002093 peripheral effect Effects 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001612 separation test Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
- B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0048—Inorganic membrane manufacture by sol-gel transition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
Definitions
- the present invention relates to a ceramic filter and, more specifically, to a ceramic filter having few defects and thin and uniform membrane thickness.
- Non-Patent Document 1 is a method where a porous membrane is formed by application on the outer surface of a heated tube substrate by the use of fabric containing silica sol with rubbing the fabric against the tube substrate.
- the hot coat method has a problem that uniform membrane cannot be formed on the entire surface of the substrate and a problem that a membrane can be formed only on the outer surface of the tube.
- the method cannot be applied to a monolith type substrate.
- a solvent present in pores of the substrate may flow out toward the membrane side upon drying after forming the membrane to cause peeling of the membrane.
- a porous membrane formed on the surface of the substrate after firing has a defect.
- the dipping method can be applied to a monolith type substrate, the number of membrane formation operations is large.
- the present invention aims to provide a ceramic filter which is formed by a small number of membrane formation operations, has few defects, has a thin and uniform membrane thickness, and high resolution.
- US2001001453 (A1 ) discloses an inorganic nanofiltration membrane with a detachment threshold between 100 and 200 daltons, which comprises: a multichannel ceramic monolith support consisting of a mixture of Al 2 O 3 and of TiO 2 , a microfiltration membrane separating layer, an ultrafiltration membrane separating layer, preferably consisting of ZrO 2 , a nanofiltration membrane separating layer, preferably consisting of ZrO 2 , and obtained by a sol-gel type method.
- US6596173 (B1 ) describes an inorganic filtering membrane characterized in that it comprises a support made of an inorganic material coated with at least a membrane separating layer consisting of metal hydroxide and/or oxide particles and at the surface of which organomineral and/or mineral units are covalently grafted.
- WO2008050813 (A1 ), which is a prior art document pursuant to Article 54(3) EPC, discloses a ceramic porous membrane formed with less membrane formation times and having less defects, a small and uniform thickness and a high flux, and a ceramic filter.
- a silica membrane (1) is formed on a titania UF membrane (14) as an ultrafiltration membrane (a UF membrane) formed on a porous base member (11) which is a microfiltration membrane (also referred to as an MF membrane) and having an average pore diameter smaller than that of the porous base member (11), and the silica membrane has an average pore diameter smaller than that of the titania UF membrane (14), and does not substantially permeates the titania UF membrane.
- JP2001212401 (A ) describes a liquid separation filter formed by depositing and forming a separation film which consists of inorganic oxide having many pores smaller in average pore size than 10 nm and being capable of permeating and separating only the specific liquid from the solution to be treated on the surface of a porous base.
- JP2001276586 discloses a separation membrane which has a gas permeability, comprises an amorphous oxide formed by Si-containing siloxane bonds and having micropores, and contains water adsorbed by the inner wall surfaces of the micropores is formed on and attached to at least one surface of a porous substrate, thus giving a gas separation filter.
- the filter is used for selectively and efficiently separating a specific gas.
- JP2005095851 (A ) provides a fluid separation filter having a chemical stability for moisture and, therefore, an excellent water resistant property with regard to separation performance.
- the fluid separation filter is formed by coating the surface of a porous supporting body with a fluid separation film containing Si-C-O bonds. Further, the fluid separation filter is formed by coating the surface of a porous supporting body with a fluid separation film containing Si-C-O bonds and, moreover, the thickness of the fluid separation filter is preferably 0.05 ⁇ m to 1 ⁇ m.
- JP2003245530 mentions a separation membrane preventing a membrane forming raw liquid from reaching at the back surface of a porous support in a membrane manufacturing process, high in the adhesiveness of the separation function membrane and thin in the porous support.
- the separation membrane is formed on the upper surface of the porous support having a rough back surface so as to extend into the porous support.
- the present inventors found out that the aforementioned problems can be solved by forming a ceramic porous membrane having an average pore size smaller than that of an ultrafiltration membrane on the ultrafiltration membrane formed on a porous substrate and having an average membrane thickness of 0.1 to 1.0 ⁇ m. That is, according to the present invention, the following ceramic filter is provided.
- a ceramic porous membrane having the average pore size smaller than that of an ultrafiltration membrane on the ultrafiltration membrane formed on the porous substrate and having an average pore size of 2 to 20 mm, which is smaller than that of the porous substrate, and an average membrane thickness of 0.1 to 1.0 ⁇ m a thin ceramic porous membrane having few defects can be formed.
- the average membrane thickness of the ultrafiltration membrane to be 0.1 to 1.0 ⁇ m, a part of the ceramic porous membrane penetrates into the ultrafiltration membrane or into the ultrafiltration membrane and the porous substrate, and thereby local segregation of the ceramic can be inhibited, and peeling off of the membrane, which is a cause of the hindrance to the separation performance, can be inhibited.
- a high flux ceramic filter having a dehydrating action with high resolution performance at low costs.
- a silica membrane as the ceramic porous membrane, it is particularly suitable for dehydration of alcohol such as ethanol and isopropyl alcohol and dehydration of organic acid such as acetic acid.
- silica membrane 10: ceramic filter, 11: porous substrate, 14: titania UF membrane, 22: partition wall, 23: cell, 25: inlet side end face, 30: coating liquid (titania sol), 31: O-ring, 32: casing, 33: vacuum pump, 40: coating liquid (silica sol), 41: masking tape
- Fig. 1 shows a partially enlarged cross-sectional view of a ceramic filter as one embodiment of the present invention.
- a titania UF membrane 14 which is an ultrafiltration membrane (UF membrane) having an average pore size smaller than that of the porous substrate 11 is formed, and, on the titania UF membrane 14, a silica membrane 1 having an average pore size smaller than that of the titania UF membrane 14 is formed.
- the porous substrate 11 is a microfiltration membrane (MF membrane) and preferably has an average pore size of 0.1 to 0.6 ⁇ m on the outermost layer.
- MF membrane microfiltration membrane
- the titania UF membrane 14 of an ultrafiltration membrane having an average membrane thickness of 0.1 to 1.0 ⁇ m (more preferably 0.1 to 0.6 ⁇ m) and an average pore size of 2 to 20 nm (more preferably 6 to 20 nm) is formed, and the silica membrane 1 having an average pore size smaller than that of the titania UF membrane 14 is formed on the titania UF membrane 14.
- the average membrane thickness of the ultrafiltration membrane is above 1.0 ⁇ m, since water permeation of ceramic sol in the ultrafiltration membrane is slow, the ceramic sol does not penetrate into the ultrafiltration membrane sufficiently, and the ceramic sol remains on the surface of the ultrafiltration membrane, and thereby local segregation is caused to easily cause peeling of the membrane. In addition, since the membrane strength of the ultrafiltration membrane is week, peeling of the ultrafiltration membrane unitarily joined with the ceramic porous membrane from the porous substrate is easily caused. On the other hand, when the average membrane thickness of the ultrafiltration membrane is below 0.1 ⁇ m, since the ultrafiltration membrane cannot cover the entire surface of the porous substrate, there is caused trouble of impossible forming of the ceramic porous membrane.
- the average thickness of a conventional titania UF membrane is 1.5 ⁇ m, and there was a problem of having segregation of silica.
- the ceramic porous membrane cannot penetrate into the pores of the ultrafiltration membrane, and local segregation of ceramic is caused on the surface of the ultrafiltration membrane to easily cause peeling of the membrane.
- the average pore size of the ultrafiltration membrane is larger than 20 nm, it seems that the ceramic porous membrane penetrates into the porous substrate to much to cause a problem that a ceramic porous membrane is not formed on the ultrafiltration membrane.
- a part of the ceramic porous membrane penetrates into the ultrafiltration membrane and the porous substrate means that the average value of the weight ratio of ceramic porous membrane material / ultrafiltration membrane material or porous substrate is 0.1 or more and that the standard deviation is 0.035 or less when measurement is performed at 10 points selected at random in the ultrafiltration membrane and the porous substrate by spot analysis by EDX element analysis.
- the average value of the weight ratio of ceramic porous membrane material / ultrafiltration membrane material or porous substrate is 0.1 or more and that the standard deviation is 0.035 or less when measurement is performed in the outermost peripheral cell position and the central cell position in each of the sites of 10%, 50%, and 90% of the entire length from an end face in the longitudinal direction of the filter.
- the ceramic filter 10 of the present invention has a monolith shape having a plurality of cells 23 partitioned and formed by partition walls 22 and forming fluid passages in the axial direction.
- each cell 23 has a circular cross section, and a silica membrane 1 as shown in Fig. 1 is formed on the inner wall surface.
- the cell 23 may be formed to have a cross section of a polygonal shape such as a quadrangle or a rectangle.
- the silica membrane 1 formed on the ceramic filter 10 can be used as a separation membrane and has high separation property for, for example, water and acetic acid.
- the porous substrate 11 serving as the substrate main body is formed as a monolith type filter element made of porous material and having a circular cylindrical shape by extrusion forming or the like.
- alumina can be used, for example, from the viewpoints of corrosion resistance, little change in pore size of the filtration portion by temperature change, and capability of obtaining sufficient strength.
- a ceramic material such as titania, cordierite, mullite, or silicon carbide can be used.
- the silica membrane 1 of the present invention is formed on the inner peripheral face (inner wall face) of the porous substrate 11, there may suitably be used a relatively long cylindrical substrate having a length of 50 cm or more or a porous substrate having a lotus root shape .
- a titania UF membrane 14 is formed, and, on the titania UF membrane 14, the silica membrane 1 is formed. That is, the ultrafiltration membrane (UF membrane) is formed on a face, where at least the silica membrane 1 is formed, of the substrate made of porous material.
- the ultrafiltration membrane is a membrane for blocking particles or polymers in the range of 0.1 ⁇ m to 2 nm, and a titania membrane is formed.
- the average pore size of the titania membrane is smaller than that of the porous substrate.
- a titania UF membrane 14 formation method there is employed, for example, a method where a membrane is formed by a filtration membrane formation method (see Patent Documents 1 and 2).
- a coating liquid (titania sol) 30 for forming the titania UF membrane 14.
- titanium isopropoxide is subjected to hydrolysis in the presence of nitric acid to obtain sol, the sol is diluted with water, and an organic binder is suitably added thereto. It is possible to dilute the sol with ethanol in place of water.
- the porous substrate 11 is disposed in a casing 32 in the state that both the end faces are sealed with O-rings 31 or the like.
- low pressure is maintained by a vacuum pump 33 on the outer peripheral side face side of the porous substrate 11 for a predetermined time to form a titania UF membrane 14 on the inner surface of the porous substrate 11.
- a thermal treatment at 500°C.
- the average membrane thickness of the titania UF membrane 14 is controlled to be 0.1 to 1.0 ⁇ m.
- the average membrane thickness of the titania UF membrane 14 can be adjusted by the titania concentration of the coating liquid (titania sol) 30. That is, the thickness of the membrane can be decreased by lowering the sol concentration, while the thickness of the membrane can be increased by raising the sol concentration. In addition, also, by repeated formation of membrane, the thickness of the titania UF membrane 14 can be increased.
- the average pore size of the titania UF membrane 14 is controlled to be 2 to 20 nm.
- the average pore size of the titania UF membrane 14 can be adjusted by the amount of the organic binder added thereto. That is, the pore size can be decreased by reducing the binder amount, while the pore size can be increased by increasing the binder amount. In addition, also, by raising the firing temperature, the pore size can be increased.
- the titania UF membrane 14 formation method may be also a general dipping method instead of the filtration membrane formation method. Though the case of using titania for the UF membrane has been described, the UF membrane is not limited to this case, and a zirconia membrane or a zeolite membrane may be employed.
- a silica membrane 1 formation method will be described by the use of Fig. 4 .
- a coating liquid (silica sol) 40 for forming the silica membrane 1.
- the coating liquid (silica sol) 40 tetraethoxysilane is subjected to hydrolysis in the presence of nitric acid to obtain sol, the sol is diluted with ethanol. It is possible to dilute the sol with water in place of ethanol.
- the outer peripheral side face of the porous substrate 11 where the titania UF membrane 14 is formed is sealed with a masking tape 41.
- the porous substrate 11 is fixed at the bottom end of a wide-mouth funnel (not illustrated), and the aforementioned coating liquid (silica sol) 40 is poured from the top portion of the substrate to pass it through the cells 23.
- a membrane formation process by general dipping may be employed instead of this method.
- temperature is raised at a rate of 100°C/hr, and, after the temperature is maintained at 500°C for one hour, temperature is lowered at a rate of 100°C/hr.
- the aforementioned operations of pouring of the coating liquid (silica sol) 40, drying, raising temperature, and lowering temperature are repeated four times.
- the titania UF membrane 14 is formed on the porous substrate 11, and the silica membrane 1 is formed on the titania UF membrane 14. That is, since the titania UF membrane 14 is formed as shown in Fig. 5B on a porous membrane 11 shown in Fig. 5A , the influence by unevenness of the surface of the porous substrate 11 is reduced by the titania UF membrane 14. Therefore, as shown in Fig. 5C , even if the silica membrane is made thin, it can be formed with few defects. Further, by controlling the average thickness of the titania UF membrane 14 to be 0.1 to 1.0 ⁇ m, the silica membrane 1 having not only high flux and low cost but also high separation performance can be obtained.
- the thus obtained ceramic filter 10 having a nano-level thin membrane-shaped silica membrane 1 formed on the inner wall surface can suitably be used as a filter for separating a mixed liquid or the like. Incidentally, by further immersing or permeating the cells 23 in acetic acid, the separation coefficient can further be improved.
- a silica membrane as the ceramic porous membrane was described.
- the substrate a monolith-shaped (outer diameter of 30 mm and length of 500 mm with 37 cells each having inner diameter of 3 mm) porous article of an alumina microfiltration membrane having an average pore size of 0.2 ⁇ m. Incidentally, both the end portions of the substrate were sealed with glass. The average pore size of the substrate was measured according to the air flow method described in ASTM F306.
- Titanium isopropoxide was subjected to hydrolysis in the presence of nitric acid to obtain titania sol.
- the sol particle diameter measured by a kinetic light scattering method was 100 nm.
- the titania sol was diluted with water, and PVA as an organic binder was suitably added thereto to obtain sol for membrane formation.
- the sol was circulated in the cells of the substrate and brought into contact with the cells to form a titania UF membrane in the cells.
- the thickness of the titania UF membrane was controlled by adjusting the titania concentration in the sol and/or the number of membrane formation operations. That is, in the case of increasing the thickness, the titania concentration in the sol was raised, and/or the number of membrane formation operations was increased. In the case of reducing the thickness, the titania concentration in the sol was lowered, and/or the number of membrane formation operations was decreased.
- the pore size of the titania UF membrane was controlled by adjusting the amount of the organic binder and/or the firing temperature. That is, in the case of increasing the pore size, the amount of the organic binder was increased, and/or the firing temperature was raised. In the case of decreasing the pore size, the amount of the organic binder was decreased, and/or the firing temperature was lowered.
- the samples were dried, they were subjected to a thermal treatment at 500°C. They served as the titania UF substrates where a titania UF membrane was formed, and the average pore size and the average membrane thickness of the titania UF membrane were measured.
- the principle of the measurement of the average pore size was the same as that of the method described in the Non-Patent Document 1, whereas water vapor and nitrogen were used in the Non-Patent Document 1, n-hexane and nitrogen were used in the measurement method used in the present invention.
- the average thickness was observed by an electron microscope. In Examples 1 to 16, as measurement results, as shown in Table 1, the average pore size was within the range from 2 to 20 nm, and the average membrane thickness was within the range from 0.10 to 1.00 ⁇ m.
- Tetraethoxysilane was subjected to hydrolysis in the presence of nitric acid to obtain silica sol, the silica sol was diluted with ethanol and adjusted to be 0.7 mass% in terms of silica to obtain a sol for forming a silica membrane.
- each sample (titania UF substrate) was sealed with a masking tape.
- the titania UF substrate was fixed at the bottom end of a wide-mouth funnel, and the silica sol of 60 ml was poured from the top portion of the substrate and passed through the cells. Incidentally, by this membrane formation step, it was confirmed that the silica membrane was formed entirely on the inner wall side.
- Drying was performed for one hour by the use of a dryer to pass a wind at room temperature through the cells of the titania UF substrate where the silica sol was poured.
- the temperature of the samples was raised at a rate of 100°C/hr, and, after the temperature was maintained at 500°C for one hour, the temperature was lowered at a rate of 100°C/hr.
- the operations of the above (6) to (8) were repeated four times to obtain ceramic filters of Examples 1 to 16.
- silica had penetrated into the titania UF membrane or into the titania UF membrane and the porous substrate. That is, by spot analysis by EDX element analysis, measurement was performed at 10 points selected at random in the titania UF membrane and the porous substrate, and it was confirmed that the average value of the weight ratio of silica / titania oxide was 0.1 or more and that the standard deviation was 0.035 or less.
- the average value of the weight ratio of silica / titania oxide was 0.1 or more and that the standard deviation was 0.035 or less also in the outermost peripheral cell position and the central cell position in each of the sites of 10%, 50%, and 90% of the entire length from an end face in the longitudinal direction of the honeycomb filter of each Example.
- Ceramic filters of Examples 17 to 32 were manufactured in the same manner as in the ceramic filters of Examples 1 to 16 except that titania was employed as the material for the porous substrates.
- Ceramic filters of Comparative Examples 1 to 4 were manufactured in the same manner as in the ceramic filters of Examples 1 to 16. As shown in Table 1, the titania UF membrane had an average pore size of 2 to 20 nm and an average thickness of 1.5 ⁇ m. At this time, silica had penetrated into neither the titania UF membrane nor the porous substrate.
- a ceramic filter of Comparative Example 5 was manufactured in the same manner as in the ceramic filters of Examples 1 to 16.
- the titania UF membrane had an average pore size of 40 nm and an average thickness of 0.6 ⁇ m.
- silica penetrated into the titania UF membrane and the porous substrate, it was found out by observation of the titania UF membrane with an electron microscope that the entire surface of the porous substrate was not covered with the titania UF membrane to allow a part of the surface of the porous substrate to be exposed.
- a ceramic filter of Comparative Example 6 was manufactured in the same manner as in the ceramic filters of Examples 1 to 16. As shown in Table 1, the titania UF membrane had an average pore size of 1 nm and an average thickness of 0.6 ⁇ m. At this time, silica had penetrated into neither the titania UF membrane nor the porous substrate.
- a pervaporation separation test was performed for two hours by circulating 90% ethanol at 70°C in the filter cells at a flow rate of 10 L/min. and vacuuming the outside of the filter to be 2 to 10 Pa.
- the permeability rate was calculated from the amount of the liquid permeated from the time after one and half hours to the time after two hours from the start of the test, and the separation coefficient ⁇ was calculated by the following formula from ethanol and water concentrations of the permeated liquid.
- ⁇ ([original liquid water mol concentration]/[original liquid ethanol mol concentration])/([permeated liquid water mol concentration]/[permeated liquid ethanol mol concentration]).
- Example 1 Structure of porous substrate Structure of ultrafiltration membrane (titania UF membrane) Property of ceramic porous membrane (silica membrane) Material Silica weight ratio in substrate Average membrane thickness [ ⁇ m] Average pore size [nm] Silica weight ratio in UF membrane Separation coefficient ⁇ Permeation rate [kg/m 2 hr]
- Example 1 Alumina 0 1.0 20 0.1 2000 2.2
- Example 2 Alumina 0 1.0 15 0.3 3000 1.8
- Example 3 Alumina 0 1.0 6 0.3 2500 1.9
- Example 4 Alumina 0 1.0 2 0.1 1500 2.4
- Example 5 Alumina 0.2 0.6 20 0.4 4000 1.6
- Example 6 Alumina 0.1 0.6 15 0.6 5500 1.4
- Example 7 Alumina 0 0.6 6 0.6 5000 1.5
- Example 8 Alumina 0 0.6 2 0.4 3500 1.8
- Example 9 Alumina 0.5 0.3 20 0.6 4000 1.8
- Example 10 Alumina 0.5 0.3 20 0.6 4000 1.8
- Example 10 Alumina
- each of Examples 1 to 32 showed higher ⁇ (separation coefficient) than that of Comparative Examples 1 to 7.
- Comparative Example 7 had the lowest a, which was merely 10.
- a mark having a size of 10 to 100 ⁇ m of peeling of the membrane was confirmed.
- silica segregated in the vicinity of the membrane peeling from the results of the surface element analysis EPMA observation In examples 5 and 7, a portion where a surface of the porous substrate was exposed was observed.
- Comparative Examples 1 to 4 had bad permeability of silica sol since the titania UF average membrane thickness was large, and the silica sol remained or silica segregation was caused on the surface of the titania UF membrane, which seems to have caused membrane peeling upon drying and firing.
- Comparative Example 5 since the titania UF pores were too large, the silica sol could not stay in the titania UF pores to have low titania UF membrane strength, which seems to have caused membrane peeling upon drying and firing.
- Comparative Example 6 since the titania UF pores were too small, it had bad silica sol permeability, and the silica sol remained or silica segregation was caused on the surface of the titania UF membrane, which seems to have caused membrane peeling upon drying and firing.
- Each of Examples 1 to 32 had smaller titania UF average membrane thickness and better permeability of silica sol than those of each of Comparative Examples 1 to 4, and thereby no silica sol remained on the titania UF membrane surface, which seems to be the reason that a homogeneous silica membrane could be formed.
- Comparative Example 7 since the titania UF membrane could not cover the entire surface of the porous substrate, the silica membrane located thereon could not cover the entire surface of the base, which seems to have caused low a.
- each of Examples 5 to 16 each of which has a titania UF average membrane thickness of 0.1 to 0.6 ⁇ m, showed higher ⁇ than that of each of Examples 1 to 4, each of which has a titania UF average membrane thickness of 1.0 ⁇ m. This seems to have been caused by the tendency of falling of ⁇ because of insufficient penetration of the silica sol into the titania UF pores and the porous substrate because the titania UF average thickness is large.
- a is high when the titania UF average pore size is 6 to 20 nm, and ⁇ is lower when the titania UF average pore size is 2 nm.
- the titania UF average pore size was too small, the silica sol hardly penetrated into the titania UF pore and the porous substrate, and the silica sol remained or silica segregation was caused on the surface of the titania UF membrane, which seems to have caused membrane peeling upon drying and firing.
- the average membrane thickness is 0.1 to 0.6 ⁇ m, and the average pore size is 6 to 20 nm.
- the average membrane thickness is 0.3 to 0.6 ⁇ m, and the average pore size is 6 to 20 nm.
- the aforementioned tendencies were observed similarly in Examples 17 to 32, where titania was used as the material for the porous substrate.
- the suitable range of the titania UF average membrane thickness is 0.1 to 1.0 ⁇ m, more preferably 0.1 to 0.6 ⁇ m, and the suitable range of the titania UF average pore size is 2 to 20 nm, more preferably 6 to 20 nm.
- a thin and uniform ceramic porous membrane can be obtained with few defects, and a ceramic filter having such a membrane formed thereon can suitably be used as a filter having high separation performance and high flux.
- a ceramic filter having a thin silica membrane of a nano-level thickness formed on the inner wall surface can be used in a site where an organic filter cannot be used, for example, separation removal in an acid or alkali solution, an organic solvent, or the like.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Claims (4)
- Filtre en céramique comprenant :un substrat poreux,une membrane d'ultrafiltration, qui est formée sur le substrat poreux et a une épaisseur moyenne de 0,1 à 1,0 µm et une taille de pores moyenne de 2 à 20 nm, etune membrane poreuse en céramique, qui est formée sur la membrane d'ultrafiltration ;dans lequel la membrane poreuse en céramique est une membrane à base de silice ;dans lequel le substrat poreux est une membrane de microfiltration ;dans lequel la membrane d'ultrafiltration est une membrane d'ultrafiltration à base d'oxyde de titane ;dans lequel la taille de pores moyenne de la membrane poreuse en céramique est inférieure à celle de la membrane d'ultrafiltration ;dans lequel une partie de la membrane poreuse en céramique a pénétré dans les pores de la membrane d'ultrafiltration, de façon que la valeur moyenne du rapport en poids matériau de membrane poreuse en céramique/matériau de membrane d'ultrafiltration soit de 0,1 ou plus et que l'écart type soit de 0,035 ou moins quand la mesure est réalisée en 10 points choisis au hasard dans la membrane d'ultrafiltration par analyse ponctuelle par analyse EDX des éléments.
- Filtre en céramique selon la revendication 1, dans lequel une partie de la membrane poreuse en céramique a pénétré dans les pores de la membrane d'ultrafiltration et du substrat poreux.
- Filtre en céramique selon la revendication 1 ou 2, dans lequel la membrane d'ultrafiltration a une épaisseur moyenne de 0,1 à 0,6 µm et une taille de pores moyenne de 6 à 20 nm.
- Filtre en céramique selon l'une quelconque des revendications 1 à 3, dans lequel le substrat poreux est une membrane en oxyde de titane ou une membrane en alumine.
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JP2008082068 | 2008-03-26 | ||
JP2008300579A JP2009255035A (ja) | 2008-03-26 | 2008-11-26 | セラミックフィルタ |
PCT/JP2009/054433 WO2009119292A1 (fr) | 2008-03-26 | 2009-03-09 | Filtre en céramique |
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KR101234490B1 (ko) | 2010-12-29 | 2013-02-18 | 이근호 | 세라믹 필터 및 그 제조방법 |
JP6043337B2 (ja) * | 2012-02-29 | 2016-12-14 | 日本碍子株式会社 | セラミック分離膜及び脱水方法 |
US20130323419A1 (en) * | 2012-06-05 | 2013-12-05 | Exxonmobil Research And Engineering Company | Methods for preparing polymer membranes on porous supports |
JPWO2014156579A1 (ja) | 2013-03-28 | 2017-02-16 | 日本碍子株式会社 | セラミック分離膜構造体、およびその製造方法 |
JP6324491B2 (ja) * | 2014-03-31 | 2018-05-16 | 富士フイルム株式会社 | ガス分離複合体およびその製造方法 |
JP6609547B2 (ja) * | 2014-03-31 | 2019-11-20 | 日本碍子株式会社 | モノリス型分離膜構造体 |
JP6677649B2 (ja) | 2014-04-11 | 2020-04-08 | スリーエム イノベイティブ プロパティズ カンパニー | 酸焼結相互接続シリカナノ粒子の3次元多孔質ネットワークを有するミクロ多孔質物品及びその製造方法 |
DE112016001282T5 (de) * | 2015-03-19 | 2017-11-30 | Ngk Insulators, Ltd. | Siliziumoxidmembran und Trennmembranfilter |
DE112016001283T5 (de) * | 2015-03-19 | 2018-01-18 | Ngk Insulators, Ltd. | Siliziumoxidmembranfilter |
US9941051B2 (en) | 2015-06-26 | 2018-04-10 | Capactor Sciences Incorporated | Coiled capacitor |
RU2616474C1 (ru) * | 2015-12-14 | 2017-04-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" | Фильтрующий материал и способ его изготовления |
WO2017153347A1 (fr) * | 2016-03-07 | 2017-09-14 | Shell Internationale Research Maatschappij B.V. | Procédé de récupération d'un composant métallique |
JP7198082B2 (ja) | 2016-03-30 | 2022-12-28 | 日本碍子株式会社 | セラミック膜フィルタ |
US20190177237A1 (en) | 2017-12-11 | 2019-06-13 | Saudi Arabian Oil Company | Ceramic membranes |
KR101993448B1 (ko) * | 2017-12-21 | 2019-06-26 | 한국화학연구원 | 수처리용 다공성 세라믹 분리막 및 이의 제조방법 |
EP3778002A4 (fr) | 2018-03-30 | 2021-12-29 | NGK Insulators, Ltd. | Matériau de base pour filtre à membrane et son procédé de production |
US20220161202A1 (en) * | 2020-11-25 | 2022-05-26 | Mott Corporation | Engineered coating for filters and methods of manufacture thereof |
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JPS61238315A (ja) | 1985-04-12 | 1986-10-23 | Ngk Insulators Ltd | 複層フイルタの製造方法 |
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US5194200A (en) * | 1991-10-08 | 1993-03-16 | Wisconsin Alumni Research Foundation | Method of creating silica ceramic membranes |
US5186833A (en) * | 1991-10-10 | 1993-02-16 | Exxon Research And Engineering Company | Composite metal-ceramic membranes and their fabrication |
US6464881B2 (en) * | 1996-10-21 | 2002-10-15 | Orelis | Inorganic nanofiltration membrane and its application in the sugar industry |
FR2771947B1 (fr) * | 1997-12-04 | 2000-02-25 | Orelis | Membrane inorganique de filtration modifiee par greffage d'organomineraux et son procede de preparation |
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JP2001276586A (ja) * | 2000-03-29 | 2001-10-09 | Kyocera Corp | ガス分離膜およびその製造方法 |
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JP4442088B2 (ja) * | 2001-12-10 | 2010-03-31 | 東レ株式会社 | 分離膜 |
JP2005095851A (ja) * | 2003-08-26 | 2005-04-14 | Kyocera Corp | 流体分離フィルタ及びその製造方法 |
US7669719B2 (en) * | 2006-07-05 | 2010-03-02 | General Electric Company | Membrane structure and method of making |
US7717272B2 (en) * | 2006-10-18 | 2010-05-18 | Ngk Insulators, Ltd. | Ceramic porous membrane and ceramic filter |
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